Protective Glove Having Textile Inner Lining

ABSTRACT

The present disclosure relates to a polymer protective glove, which includes a textile lining and a polymer layer having an elastomer with isoprene units. According to the present disclosure, the textile lining or textile layer and the polymer layer are embodied in the form of a layered laminate. The present disclosure also relates to a method for manufacturing such a protective glove.

TECHNICAL FIELD

The present disclosure relates to protective gloves, in particularelastic, polymeric protective gloves with a textile lining, as well asto a method for their manufacture.

BACKGROUND

Because of the availability of a number of suitable polymers, it ispossible to obtain protective gloves for a large number of chemicalsubstance classes. It is thus possible, depending on the polymer orpolymeric composite materials used, to obtain long permeation times fordifferent substance classes. In particular, elastomers such as isoprenerubbers also feature a low gas permeability, which is desirable from asafety standpoint. Consequently, however, protective gloves composed ofpolymeric materials are not breathable, i.e. the moisture generated byperspiration remains inside the glove. This has a significant negativeimpact on the wearing comfort of such a protective glove, particularlywhen it is worn for long periods. To improve the wearing properties, inparticular to absorb moisture, therefore, textile inner gloves aregenerally used. The use of a textile inner glove and a separatepolymeric protective glove, however, is disadvantageous for practicalreasons. On the one hand, it takes a relatively long time to put on theinner glove and the protective glove. On the other hand, the use of twogloves results in a relatively large overall thickness of the glovecombination, which has a disadvantageous effect on tactile sensitivity.There is also often a lot of play, i.e. space between the textile innerglove and the polymeric glove, which likewise has a disadvantageouseffect on tactile sensitivity.

There is thus an interest in polymeric protective gloves with a fixedtextile lining. In this connection, there are protective gloves knownfrom the prior art in which the textile lining is glued into the polymerprotective glove, i.e. an adhesive agent is used to affix the lining inthe glove. The textile lining and the polymeric material, however, donot have a common phase boundary and the adhesion is produced by meansof the adhesion and cohesion forces of the adhesive agent, for example aglue. The gluing process is disadvantageously complex and the textilelining and polymer glove come unglued from each other relatively easily.The latter is particularly true when the bonding agent is washed outover the course of the wearing life or is subject to other externalinfluences.

By contrast, a protective glove made of a composite material composed ofa textile knitted fabric and a polymer layer has a more powerfuladhesion between the textile knit and the polymer layer.

German patent disclosure DE 27 59 008 A1 describes a protective glovecomposed of a textile that has been coated by means of a dip-coatingprocess from a dispersion with polymers such as polyvinyl chloride (PVC)and also describes its manufacturing method and an apparatus conceivedfor this purpose. Due to the irregular layer thicknesses and theoccurrence of diffusion conduits, so-called “pin holes,” a protectiveglove of this kind has a comparatively poor protective effect. This isalso disadvantageous from an economic standpoint because it results in alarger number of rejects. It also requires the use of additives such ascoagulation reagents.

GENERAL DESCRIPTION

The object of the present disclosure is to create a polymeric protectiveglove with a textile lining, which has uniform permeation times acrossthe entire surface of the glove and thus has a reliable protectiveeffect in relation to a variety of chemical compound classes.

Another object is to create a glove of this kind that also has a highlevel of wearing comfort while maintaining flexibility and tactilesensitivity. Another object is to create an efficient method formanufacturing a protective glove of this kind.

This object is attained by the subject of the independent claims. Otherembodiments and modifications are disclosed in the respective dependentclaims.

Accordingly, the present disclosure provides a polymeric protectiveglove with a textile lining in which the textile lining and at least afirst polymer layer are embodied in the form of a layered laminate. Thefirst polymer layer includes a synthetic elastomer, which is embodied inthe form of a copolymer with isoprene as a monomer unit, i.e. theelastomer contains isoprene monomer units. In the context of the presentdisclosure, copolymers are understood to be polymers with at least twodifferent monomer units. An isoprene monomer unit is understood inparticular to be the repeating unit I. Polymers with isoprene monomerunits are understood to also include those polymers in which derivativesof isoprene monomer units are present. In particular, such polymers areunderstood to be polymers with isoprene monomer units in which aderivatization has taken place by means of polymer analogous reactionssuch as halogenation of the polymer.

The textile layer of the layered laminate forms the inside of the gloveand is understood to be the bottom (innermost) layer. Consequently, thefirst polymer layer, like optional, subsequent additional polymer layerssituated over the said layer, i.e. relative to the glove as it is wornby the user, is situated toward the outside. The layered laminate isconstructed so that the textile layer and the first polymer layer arefirmly bonded to each other by means of a common boundary layer. Thetextile layer here can, for process-related reasons, also containadditives or residual amounts of additives such as sizing agents orfilm-forming substances, in particular polyvinyl alcohol (PVA) or apolysaccharide such as starch.

In a preferred embodiment of the present disclosure, the textile layerand the first polymer layer are held together by a fiber reinforcedmaterial layer, i.e. a fiber/synthetic composite. This permits goodadhesion of the first polymer layer to the textile lining or textilelayer. In particular, it is thus possible to dispense with using anadhesive agent, in particular a glue. The textile properties of thetextile lining are thus largely preserved.

On the common boundary layer, the lining and polymer layer form a fiberreinforced material in which the fibers of the textile layer areembedded into a matrix of the polymer of the first polymer layer. Thefiber reinforced material is produced when the textile lining or textilelayer is dipped into a solution of a synthetic rubber with isoprenemonomer units. At the boundary layer of the two layers, the polymersolution penetrates into the textile layer and envelops the fibers. Thetextile layer is thus at least partially penetrated by the polymerlayer. An entanglement of the textile fibers with the polymer chainsoccurs. This increases the contact area between the fibers and thepolymer chains and thus also increases the inter- and intramolecularforces of attraction that can be due to interactions such asvan-der-Waals forces or adhesion effects.

Preferably, the textile lining is composed of a knitted fabric. It maybe desired that, in addition to the first polymer layer, the textilelayer or textile lining is elastic.

The knitted fabric is preferably a knitted fabric with double loops; aninterlock knitted fabric is particularly preferable. This may produce afiber reinforced material while preserving the textile properties of thelining since the knitted fabric has a sufficient mesh density, which hasa positive effect on the degree of impregnation of the textile lining.

In an embodiment of the present disclosure, the knitted fabric of thetextile lining contains cellulose-containing fibers. It may be desiredthat the knitted fabric is composed of cotton or a cotton blend fabric,in particular with a cotton content of greater than 50%. This may bedesirable because natural fibers, in particular cellulose-containingfibers, are particularly able to absorb moisture due to their swellingcapacity.

In an embodiment, the cotton fabric has a density of greater than 150g/m², in particular greater than 250 g/m². The yarn size of the yarnused is preferably 30:1. It has turned out that the penetration of thetextile lining can be influenced by means of the density of the knittedfabric in combination with the yarn size.

In one embodiment of the present disclosure, the first polymer layercontains an elastomer with butyl monomer units. It is thus possible toachieve a protective effect in relation to a multitude of compoundclasses. Thus, elastomers with isoprene monomer units such ascross-linked butyl rubbers (IIR), in particular elastomers with butylmonomer units, have a good protective effect in relation to polarsolvents and in relation to acids and bases. Low glass temperaturesT_(g) result in a very good flexibility, even at low temperatures.Moreover, elastomers with isoprene units have a low gas permeability,i.e. they are impermeable to a multitude of gases such as hydrogenchloride or ammonia.

In a preferred embodiment of the present disclosure, the first polymerlayer contains an elastomer with halogenated butyl monomer units, inparticular an elastomer with butyl monomer units that has beenhalogenated in a polymer analogous reaction. It is particularlypreferable for the first polymer layer to contain an elastomer withbromobutyl monomer units; in the context of the present disclosure,bromobutyl monomer units are understood in particular to be therepeating units II, III, and IV.

Compared to their pure hydrocarbon derivatives, halogenated butylrubbers are easier to cross-link because of their lower bond energies.This effect is particularly pronounced in rubbers with bromobutylmonomer units. In addition, a halogenation of the butyl rubber increasesits chemical inertness and thus increases the protective effect of theglove.

According to one embodiment of the present disclosure, the first polymerlayer is applied to the textile layer by means of a dip-coating process,i.e. a dipping process, in particular a dip-coating process from asolution. This makes it possible to dispense with additives such ascoagulation reagents. In addition, polymer layers applied by dip-coatingprocesses from solutions have consistent layer properties. It is therebypossible to ensure constant permeation times over the entire glove andthus a reliable protection. It is likewise possible to avoid theoccurrence of so-called pin holes, i.e. diffusion conduits, in thepolymer layer.

Preferably, the first polymer layer is composed of two polymersublayers: the first polymer sublayer contains no colorant, the secondpolymer sublayer contains colorant, and the second polymer sublayer isdisposed onto the first polymer sublayer. This embodiment of the firstpolymer layer may provide uncolored, i.e. light-colored, textile liningsthat are typically used for protective gloves. Because an uncoloredfirst polymer sublayer is used, the sublayer glistens through thetextile lining without influencing the color impression of the lining.On the other hand, users especially prefer protective gloves in whichcolorants have been added to the polymer layer; hence, the establishedposition of such gloves in the marketplace.

In another modification of the present disclosure, at least one secondpolymer layer of another, different polymer is applied over the firstpolymer layer. In another preferred embodiment, the second polymer layercontains a fluorinated elastomer. Repulsive, i.e. repelling,interactions sharply reduce an adsorption of molecules on the layersurface, thus increasing the resistance to a large number of chemicalsubstance classes. Consequently, the comparatively high grease, oil, andfuel permeability of the first polymer layer's elastomer with isoprenemonomer units can be compensated for through combination with the secondpolymer layer.

Such a protective glove made of a composite material of differentpolymer layers, in particular a layered laminate composed of an isopreneelastomer and a fluoroelastomer, due to synergistic effects, offers abroader range of protection, i.e. high permeation times for a largenumber of compound classes, than corresponding protective gloves withonly one polymer layer.

In yet another modification of the present disclosure, the secondpolymer layer contains an elastomer with 1,1-difluoroethylene monomerunits. Fluoroelastomers with 1,1-difluoroethylene monomer units areinert in relation to many chemicals, oils, and fuels and are heatresistant. The high tear resistance of up to 20 MPa of fluororubberswith 1,1-difluoroethylene monomer units also results in a highmechanical resistance of the polymer composite material.

In a further embodiment of the present disclosure, the second polymerlayer contains a copolymer with the monomers 1,1-difluoroethylene andhexafluoropropene.

In another preferred embodiment according to the present disclosure, thesecond polymer layer contains an elastomer with acrylonitrile monomerunits such as a cross-linked nitrile rubber (NBR).

Preferably, the protective glove has a first polymer layer with athickness of 0.05 mm to 0.5 mm and/or a second polymer layer with athickness of 0.05 mm to 0.15 mm. This has a good effect on permeationtimes, flexibility, and wearing comfort.

The manufacturing method is composed of at least the following steps:

In step a), a textile lining is placed onto a glove form. In this case,an anti-friction agent may be used, such as a silicone oil, which isapplied to the glove form in advance. In the next step b), a solution ofa film-forming polymer is applied to the textile lining that has beenplaced onto the glove form. In order to produce a first polymer layer,in step c), a glove form is dipped into a first solution of a synthetic,first rubber. In order to prevent a cross-linking of the rubber eitherin the solution or immediately after removal of the form, thetemperature T₁ during the dip-coating procedure is lower than thecross-linking temperature of the first rubber. After a predefineddipping time, i.e. immersion time, the glove form is removed from thefirst solution (step d)). Steps c) and d) are carried out once orseveral times in sequence. The dipped first polymer layer is dried (stepe)). Preferably, the drying time is at least 8 hours. Then in step f),the first polymer layer is vulcanized by autoclaving the protectiveglove. In the next step g), the protective glove is removed from theform.

In another embodiment of the method according to the present disclosure,in step c), the glove form is dipped into a first solution of a butylrubber, preferably a first solution of a halogenated butyl rubber, andparticularly preferably a first solution of a rubber with bromobutylmonomer units.

In a modification of the present disclosure, after step e), the gloveform is dipped into a second solution of a second, other syntheticrubber. After a predefined dipping time t₂, the glove form is removedfrom the solution and dried. In particular, the first and second polymerlayers are jointly vulcanized in step f).

The second solution may contain a rubber with the monomers1,1-difluoroethylene and/or hexafluoropropene. This has a positiveeffect on the properties of the glove, for example on the permeationtimes for a multitude of chemical compound classes.

Usually in the solvent dipping process, i.e. a dip-coating process froma solution, however, longer immersion times are required than in thecorresponding dispersion process. When a textile lining is dipped for along time, this typically results in a partial or even total penetrationof the textile lining and thus in a loss of the desired textileproperties of the lining. Pre-treating the lining with a film-formingpolymer can prevent a complete impregnation of the textile lining, evenwith longer dipping times. It is thus possible to dip polymer layersinto solutions while still maintaining the desired textile properties ofthe lining.

In particular, polar polymers with hydroxyl groups are used asfilm-forming polymers. Preferably, these polymers are water-soluble. Inparticular, a PVA solution and/or a polysaccharide-containing solutionsuch as a starch-containing solution are used as a solution of afilm-forming polymer. Preferably a plasticiser, in particular glycerin,is added to the film-forming polymer solution.

Surprisingly, it occurred that according to one embodiment, a sprayingor a single or multiple brushing or dabbing of the textile lining with acloth impregnated with the solution of the film-forming polymer canprevent a complete penetration with the rubber solution. It is thuspossible to prevent a complete penetration of the textile lining. Thiseffect is particularly pronounced with cellulose-containing textiles.Cellulose-containing fibers such as cotton fibers swell significantly inthe presence of moisture and absorb the moisture. The application of thefilm-forming polymer thus makes it possible to optimally pre-treat thesefibers for the subsequent dip-coating procedure.

In one embodiment, before being dipped into the first solution of arubber with isoprene units, the textile lining is brushed with the PVAsolution until the amount of application of PVA onto the lining totals0.15 to 3 g, preferably 0.3 to 1.8 g, particularly preferably 0.6 to 0.9g. It is thus possible to influence the degree to which the rubberimpregnates the textile lining.

According to an alternative embodiment, the textile lining is sprayedwith a solution containing a polysaccharide such as starch. Thissolution preferably functions as a sizing agent. The use of apolysaccharide, in particular starch, as a film-forming polymer has theadvantage that the protective glove does not stick very powerfully tothe glove form. As a result, after production, the glove cansurprisingly be removed from the glove form even without turning itinside out, which significantly improves the production process.

In one embodiment of the method according to the present disclosure, theviscosity of the first rubber solution is from 100 to 200 s (determinedwith a 6 mm Ford beaker). This is good because a rubber solution with ahigh viscosity, due to its flow behavior, penetrates more slowly intothe textile lining than corresponding solutions with lower viscosities.Consequently, the selection of the viscosity of the first rubbersolution constitutes a further parameter which, in combination with thefilm-forming polymer, can be used to influence the degree ofpenetration.

In a modification of the present disclosure, the textile lining isdipped into two different solutions of the same first synthetic rubber,which differ in terms of their viscosities. First, the textile lining isdipped according to process steps c) and d) into a solution of the firstsynthetic rubber with a high viscosity. This produces a first polymersublayer, which does not completely penetrate the textile layer andseals the surface of the textile lining on the outside. In thesubsequent dip-coating according to process steps c) and d), the dippingtakes place in a second solution of the first synthetic rubber with alower viscosity, thus contributing to a further build-up of the firstpolymer layer. This is good for process-related reasons since rubbersolutions with comparatively low viscosities are easier to work withwhen dip-coating from a solution.

In at least one of the dip-coating procedures, the glove form ispreferably dipped partially at least once and then is dipped all theway. This makes it possible to achieve uniform layer thicknesses alsowith glove forms in which this would not otherwise be possible due totheir geometry, for example in glove forms with sleeves that widen outin the direction of the glove opening. The partial dipping is alsodesired in terms of the degree of penetration of the textile layer. Byinitially pre-dipping only the hand region, it is possible to select areduced dipping depth. As a result, the hydrostatic pressure is lowerduring the first dip-coating procedure. This effect is particularlyobservable at the finger tips. Each dip-coating procedure of the gloveform into the same rubber solution produces another layer of the rubber,which is referred to as a dipped polymer sublayer. After a dippedpolymer sublayer has been deposited in the first partial dippingprocedure, which seals the textile lining up to approximately the wrist,then a full dipping can occur, i.e. with a higher hydrostatic pressureat the fingers, without this disadvantageously affecting theimpregnation depth of the textile lining.

A preferred embodiment of the present disclosure provides a method inwhich the polymer layers are dipped as often and for as long asnecessary until the first polymer layer has reached a thickness of 0.05to 0.5 mm and/or the second polymer layer has reached a thickness of0.05 to 0.2 mm.

The vulcanization of the first polymer layer preferably occurs by meansof autoclaving at a pressure of 3 to 5 bar and/or at a temperature of 60to 170° C., in particular at a temperature of 90 to 150° C. Across-linking of rubbers into elastomers increases their mechanicalresistance significantly. In addition, the cross-linking reduces thepermeation rates within the cross-linked polymer layers.

The removed protective gloves may be washed with water to which tensideshave preferably been added. Residues of PVA and/or starch that are notenveloped by the first polymer layer can thus be at least partiallyremoved from the textile lining. However, one advantage in the use ofstarch as a film-forming polymer lies in the fact that it is possible todispense with the use of rinsing agents when removing the protectiveglove from the glove form. Furthermore, the starch can remain in thetextile lining without a significant, negative impact on the wearingcomfort, so that it is possible to dispense with an additional step ofwashing out the finished protective glove, thus making it possible toincrease productivity.

The present disclosure will be described in greater detail below inconjunction with an illustrative embodiment and with reference to thefigures; some elements that are the same or similar have been providedwith the same reference numerals.

BRIEF DESCRIPTION OF THE FIGURES

FIG. 1 is a schematic depiction of the manufacturing method of the firstillustrative embodiment,

FIG. 2 is a schematic depiction of the manufacturing method of thesecond illustrative embodiment,

FIG. 3 is a schematic depiction of the manufacturing method of the thirdillustrative embodiment,

FIG. 4 is a schematic depiction of the protective glove according to thepresent disclosure,

FIG. 5 is a schematic cross-section through the composite material of aprotective glove with the glued-in textile lining,

FIG. 6 is a schematic cross-section through the detail A of the firstillustrative embodiment,

FIG. 7 is a schematic cross-section through the detail A of the secondillustrative embodiment, and

FIG. 8 is an optical microscope image of the cross-section through thedetail A of the first illustrative embodiment.

DETAILED DESCRIPTION

FIG. 1 schematically depicts the manufacturing method of a protectiveglove 16 in conjunction with the first illustrative embodiment. FIG. 2shows a simplified form of the manufacturing method, which is explainedin greater detail in conjunction with a second illustrative embodiment.FIG. 3 shows another embodiment of the manufacturing method. FIG. 4 is aschematic depiction of the protective glove 16 according to the presentdisclosure. The upper part of the protective glove 16 is composed of thefingers 17, the palm, and the back of the hand and at the wrist 18,transitions into the sleeve 19 of the glove. The inside of theprotective glove 16 is composed of the textile lining 2. The layerstructure of the layered laminate of the two illustrative embodimentswill be described in greater detail in conjunction with detail A inFIGS. 5 and 7.

The method schematically depicted in FIG. 1 for manufacturing the firstillustrative embodiment includes the following steps:

A glove form 1 composed of ceramic is brushed with silicone oil. Then atextile cotton lining 2 is pulled on over the glove form 1. A cloth thatis impregnated with a PVA solution is used to apply 3 to 4 coats of theaqueous PVA solution 3 to the textile lining 2. To produce the PVAsolution 3, first 3.75 kg of PVA are dissolved in 25 liters ofdemineralized water at 90° C. For the ready-to-use solution 3, 1 literof the parent solution was mixed with 500 ml glycerin and 5 liters ofdemineralized water. The PVA solution 3 is in particular applied fromthe finger tips 20 to the wrist 18 by wiping with a cloth, leaving outthe sleeve of the glove 19. Then the lining is dried at roomtemperature. In a heated dipping case 4, the glove form 1 is dipped intoa dipping reservoir 5 of a first solution of a synthetic first rubber 6.The solution temperature of the solution of the synthetic first rubber 6is T₁=30° C. during the dipping.

The first solution of a synthetic first rubber 6 contains bromobutylrubber and toluene as a solvent. No colorants were added to the firstbromobutyl solution 6. The first bromobutyl solution 6 has a viscosityof 100 to 200 s (determined with a 6 mm Ford beaker) during the dipping.In a first dip-coating procedure, the glove form 1 is partially dippedinto the first bromobutyl solution 6 from the finger tips 19 to thewrist 18 and in the subsequent dip-coating procedures, is dipped into itall the way, i.e. including the sleeve 19. In the first dip-coatingprocedure, the partial dipping causes a lower hydrostatic pressure toact on the textile lining, in particular on the fingers 17 and thefinger tips 20, than would occur in a complete dipping. It is thuspossible to reduce the penetration of the textile lining 2 by the firstbromobutyl solution 6. After the drying of the first dipped polymersublayer thus produced, the surface of the textile lining 2 is sealed,thus permitting the dipping in subsequent dip-coating procedures to becarried out with higher hydrostatic pressure at the fingers 17 and thefinger tips 20. The dipping is carried out as often and for as long asnecessary until the dipped polymer sublayers produced in the individualdipping procedures combine to reach a thickness of approximately 0.1 mmand thus constitute the first polymer sublayer 26 of the first polymerlayer 25. For the dipping of the glove form 1 in the bromobutyl solution6, the lifting device 7 raises and lowers the dipping reservoir 5. Aftereach dip-coating procedure, the glove form 1 is dried under rotation fora period of 30 minutes at 30° C.

The polymer layer 26 deposited in the first bromobutyl solution 6 andcomposed of a plurality of polymer dipped sublayers (not shown in detailin FIGS. 6 and 7) is white. The glove form 1 is dried for at least 8hours at 25 to 30° C. in order to remove the solvent.

Then, in a second heatable dipping casing 8, a dip-coating in a secondsolution 10 of the synthetic first rubber contained in a dippingreservoir 9 is carried out. The solution temperature of the secondrubber solution 10 is 30° C. The second solution of the synthetic firstrubber 10 thus likewise contains bromobutyl rubber dissolved in toluene.In addition, the second bromobutyl solution 10 contains carbon as acolorant. The viscosity of the second bromobutyl solution 10 is from 50to 120 s (determined with a 6 mm Ford beaker). The glove form 1 isdipped into the second bromobutyl solution 10 in three full-immersiondip-coating procedures until the dipped polymer sublayers deposited inthis way (not shown in detail in FIGS. 6 and 7) combine to produce thesecond polymer sublayer 27 of the first polymer layer 25 and have athickness of approximately 0.05 mm. After each dipping procedure, theglove form 1 is dried under rotation. After the last dip-coatingprocedure in the second bromobutyl solution 10, the glove form 1 isdried for 12 hours at room temperature.

Then in a heatable dipping casing 11, the glove form 1 is dipped into adipping reservoir 12 containing a third rubber solution 13. Here, too,the glove form 1 is not moved, but instead, the lifting device 7 movesthe dipping reservoir 12. The third solution of a synthetic third rubber13 contains a rubber with the monomers 1,1-difluoroethylene,hexafluoropropene, and tetrafluoroethylene, e.g. Viton®. Methyl ethylketone is used as a solvent. The temperature T₂ of the Viton® solution13 is T₂=25° C. during the dip-coating procedure.

After a predefined dipping time, the glove form 1 is removed from thedipping reservoir 12 and dried for 30 minutes at a temperature of 25° C.under rotation in the dipping casing 11. The above-described process ofdipping in the Viton® solution 13 and the subsequent drying procedureare repeated 3 to 5 times until the layer thickness of the Viton® layerserving as the second polymer layer 27 is approximately 0.1 mm. In orderto remove the methyl ethyl ketone completely, the glove form 1 is driedfor 12 hours at room temperature. Then, the coated glove form 1 isvulcanized in an autoclave 14 for 120 minutes at a pressure of 3 bar anda temperature of 150° C. Thus, the first polymer layer 25 and the secondpolymer layer 28 are jointly vulcanized as a layered laminate 29composed of different polymers.

FIG. 2 shows the manufacturing method of a second illustrativeembodiment. The second illustrative embodiment has only the firstpolymer layer 25 and thus constitutes a simplified form of the firstillustrative embodiment described above. Here, too, the manufacturingmethod includes preparing the glove form 1, pulling on the textilelining 2, and coating it with a PVA solution 3. These steps areperformed in accordance with the manufacturing method of the firstillustrative embodiment. By contrast with the first illustrativeembodiment, however, dipping is only carried out in the bromobutylsolutions 6 and 10 according to the manufacturing method of the firstillustrative embodiment. After the last dip-coating procedure in thebromobutyl solution 10, the glove form 1 is dried at room temperature tocompletely remove the methyl ethyl ketone. The coated glove form 1 isthen vulcanized in an autoclave 14 for 120 minutes at a pressure of 3bar and a temperature of 150° C.

FIG. 3 shows a third illustrative embodiment of the manufacturingmethod. The difference from the first illustrative embodiment (FIG. 1)lies in the use of a starch-containing solution 15 in lieu of the PVAsolution 3. For example, the starch-containing solution is aconventional ironing or laundry starch solution thinned 1:1 with water.Consequently, it is preferable for PVA and/or starch to be used as thepolar polymer with hydroxyl groups. Before the first dip-coatingprocedure, the textile lining 2 in this case is sprayed with thestarch-containing solution and is then dried in an oven (30) until thewater of the starch-containing solution has completely evaporated, for20 minutes at 80° Celsius in the example. The subsequent process stepsare performed analogously to the first illustrative embodiment.

The layer structure of the first illustrative embodiment isschematically depicted in FIG. 6; dipped polymer sublayers are not shownin detail. The protective glove 16 according to the present disclosureand the composite material according to the present disclosure arecomposed of a textile layer or the textile lining 2 and the firstpolymer layer 25, which partially penetrates the textile layer 2.Consequently, unlike the protective glove with the glued-in lining 2schematically depicted by way of example in FIG. 5, the compositematerial according to the present disclosure does not have a adhesiveagent layer 22. The partial penetration of the textile lining 2 by thefirst polymer layer 25 produces a mechanical entanglement of fibers andrubber, which is fixed in place in place by the vulcanization of therubber. In this case, the penetration only goes so deep, as a result ofwhich the textile properties of the lining 2 are at least partiallypreserved.

The textile layer or textile lining 2 forms the inside of the glove. Thearrow 23 symbolizes the chemical action on the protective glove 16 fromthe outside.

In the first illustrative embodiment, in addition to the textile layer 2and the first polymer layer 25, which is composed of the two polymersublayers 26 and 27, the layered laminate of the protective glove 16 isalso composed of a second polymer layer 28, as schematically depicted inFIG. 6.

The textile lining 2 of the illustrative embodiment contains cottonfibers. The cotton content is >50%; the lining can be a cotton blendfabric or a pure cotton knitted fabric. The knitted fabric is embodiedas an interlock knitted fabric and has a weight of 265 g/m² with a yarncount of 30.

The first polymer layer 25 is composed of bromobutyl rubber and has alayer thickness of 0.15 mm. This bromobutyl layer 25 not only acts as abarrier to liquid media, but also has a very low gas permeability.Consequently, the bromobutyl layer 25 provides protection from gasessuch as ammonia or hydrogen chloride. The second polymer layer 28contains a fluoroelastomer with the monomers 1,1-difluoroethylene andhexafluoropropene and possibly also tetrafluoroethylene, e.g. Viton®.The Viton® layer 28 has a layer thickness of 0.1 mm. The combination ofthe bromobutyl layer 25 and the Viton® layer 28 in the layered laminate29 makes it possible to achieve a protective effect that goes beyond thecumulative action of the two individual layers. The illustrativeembodiment has long permeation times for a multitude of compound classessuch as aliphatic hydrocarbons, acids, bases, and polar organiccompounds such as amines and polar solvents. The textile lining 2simultaneously ensures a high level of wearing comfort without having anegative impact on tactile sensitivity or flexibility of the protectiveglove 16.

FIG. 8 shows an optical microscope image of the cross-section A of thesecond illustrative embodiment described above. The textile lining 2forms the inside of the glove. The bromobutyl layer 25 and the textilelining 2 thus form a composite material. The white, i.e. uncolored,first bromobutyl sublayer 26 here partially penetrates the textile layer2 and seals the textile lining 2 from the outside. The second bromobutylsublayer 27 that is colored with carbon is visible over the firstbromobutyl sublayer 26.

It is clear to the person skilled in the art that the above-describedillustrative embodiment is to be understood as an example and that theinvention is not limited to this, but can be varied in numerous wayswithout going beyond the scope of the invention. It is also clear thatthe features—regardless of whether they are disclosed in thedescription, the claims, the figures, or in some other way—also defineindividual, components of the present disclosure, even if they aredescribed together with other features.

1. A polymeric protective glove with a textile lining, characterized in that the protective glove 2 includes a textile layer embodied in the form of a textile lining and at least one first polymer layer including a synthetic elastomer with isoprene units and in which the textile layer and the first polymer are embodied in the form of a layered laminate and the inside of the protective glove is formed by the textile layer.
 2. The protective glove according to claim 1, wherein the textile lining and the first polymer layer constitute a fiber reinforced material at their boundary layer.
 3. The protective glove according to claim 1, wherein the textile lining and the first polymer layer are held together without an adhesive agent.
 4. The protective glove according to claim 1, wherein the textile lining is a knitted fabric, preferably a knitted fabric with double loops, particularly preferably an interlock knitted fabric.
 5. The protective glove according to claim 4, wherein the knitted fabric contains cellulose-containing fibers.
 6. The protective glove according to claim 4, wherein the knitted fabric forms a textile lining including a cotton knitted fabric or a cotton blend knitted fabric, in particular a cotton blend knitted fabric with a cotton content of >50%.
 7. The protective glove according to claim 1, wherein the textile layer has a density of >150 g/m2, in particular >250 g/m2
 8. The protective glove according to claim 1, wherein the first polymer layer contains an elastomer with butyl monomer units.
 9. The protective glove according to claim 1, wherein the first polymer layer contains an elastomer with halogenated butyl monomer units, in particular bromobutyl monomer units.
 10. The protective glove according to claim 1, wherein the first polymer layer is including a layered laminate containing at least two sublayers of the same polymer.
 11. The protective glove according to claim 10, wherein the first sublayer of the first polymer layer contains no colorant and the second sublayer contains colorant.
 12. The protective glove according to claim 1, wherein the first polymer layer has been applied by means of a dip-coating process, in particular by means of a dip-coating process from a solution.
 13. The protective glove according to claim 1, wherein at least one second polymer layer of a second synthetic elastomer is disposed onto the first polymer layer.
 14. The protective glove according to claim 13, wherein the second polymer layer contains an elastomer with i) 1,1-difluoroethylene and/or hexafluoropropene monomer units or ii) acrylonitrile monomer units.
 15. The protective glove according to claim 1 or 13, wherein the first polymer layer has a thickness of 0.05 mm to 0.5 mm and/or the second polymer layer has a thickness of 0.05 mm to 0.15 mm. 20
 16. The protective glove according to claim 1, wherein the textile layer contains at least residual amounts of a film-forming polymer, in particular polyvinyl alcohol and/or a polysaccharide, preferably starch.
 17. A method for manufacturing a protective glove having at least the following steps: a) placement of a textile lining onto a glove form, b) application of a solution of a film-forming polymer onto the textile lining and drying of the textile lining, c) dipping of the glove form into a first solution of a synthetic, first rubber at a temperature T1, where T1 is lower than the cross-linking temperature of the first rubber, in order to produce a first synthetic polymer layer, d) removal of the glove form from the first rubber solution after a predefined dipping time, with steps c) and d) being carried out once or several times in sequence, e) drying of the dipped first synthetic polymer layer until the solvent is at least largely evaporated, f) vulcanization of the first synthetic polymer layer by autoclaving the protective glove, g) removal of the protective glove from the glove form.
 18. The method according to claim 17, wherein the synthetic rubber of the first solution is a butyl rubber, preferably a halogenated butyl rubber, and particularly preferably a bromobutyl rubber.
 19. The method according to claim 17, wherein after step e), the glove form is dipped into a second solution of a second synthetic rubber and after a predefined dipping time t2, is removed from the second solution and dried.
 20. The method according to claim 19, wherein the second synthetic rubber of the second solution is halogenated.
 21. The method according to claim 19, wherein the second synthetic rubber of the second solution contains the monomers 1,1-difluoroethylene and/or hexafluoropropene.
 22. The method according to claim 17, wherein the film-forming polymer contained in the film-forming polymer solution is a polar, preferably water-soluble polymer with hydroxyl groups.
 23. The method according to claim 17, wherein the solution of the film-forming polymer contains polyvinyl alcohol and/or a polysaccharide, in particular starch.
 24. The method according to claim 17, wherein a plasticiser, in particular glycerin, is added to the film-forming polymer solution.
 25. The method according to claim 23, wherein the textile lining is brushed with the PVA solution (3) until the amount of application of PVA totals 0.15 to 3 g, preferably 0.3 to 1.8 g, particularly preferably 0.6 to 0.9 g.
 26. The method according to claim 17, wherein the viscosity of the first rubber solution is from 100 to 200 s, determined with a 6 mm Ford beaker.
 27. The method according to claim 17, wherein the glove form is first dipped into the first solution of the first synthetic rubber and is then dipped into a second solution of the first synthetic rubber and the viscosity of the first solution is greater than the viscosity of the second solution.
 28. The method according to claim 17, wherein in at least one of the dip-coating procedures, the glove form is partially pre-dipped to the wrist at least once and then is dipped completely.
 29. The method according to claim 17 or 19, wherein the glove form is dipped for as long and as often as necessary into the corresponding rubber solutions until the first polymer layer has reached a thickness of 0.05 to 0.5 mm and/or the second polymer layer has reached a thickness of 0.05 to 0.2 mm.
 30. The method according to claim 17, 19, or 27, wherein the protective glove, after the dipping procedures in the first rubber solution or in the various rubber solutions, is vulcanized in step f) at a pressure of 3 to 5 bar and/or a temperature of 60 to 170° C., preferably 90 to 150° C. 